KR101015327B1 - Aggregate of fibrous columnar structures and pressure-sensitive adhesive member using the same - Google Patents

Abstract

Provided is a fibrous columnar structure assembly having excellent mechanical properties, high specific surface area, and good adhesive properties. Provided is a fibrous columnar structure assembly having excellent heat resistance, high specific surface area, and excellent adhesive properties under temperature conditions from room temperature to high temperature. A fibrous columnar structure assembly having a high specific surface area and adhesive properties in which adhesion to different adherends having different surface free energies does not change (no adherend selectivity) is provided. An adhesive member using such a fibrous columnar structure assembly is provided.
The fibrous columnar structure assembly 1 of the present invention includes a fibrous columnar structure having a plurality of diameters, and the distribution width of the diameter distribution of the fibrous columnar structure having the plurality of diameters is 10 nm or more, and the diameter distribution thereof. The relative frequency of the mode of is less than 30%.

Description

FAGROUS COLUMNAR STRUCTURES AND PRESSURE-SENSITIVE ADHESIVE MEMBER USING THE SAME}

The present invention relates to a fibrous columnar structure assembly and its use. More specifically, the present invention relates to a fibrous columnar structure assembly having excellent mechanical properties and high specific surface area, and an adhesive member using the same.

In industrial applications, adhesives having various properties are used. However, most of these materials are viscoelastic bodies that are flexibly bulk designed. Since the adhesive agent which consists of viscoelastic bodies is low in modulus, it is wet with an adherend, and is affinity, and expresses adhesive force.

On the other hand, it is known that a columnar fiber structure having a fine diameter exhibits adhesive properties as a novel adhesive. Since it has the diameter of a micro order and a nano order, it is known to follow the surface unevenness | corrugation of a to-be-adhered body, and to express adhesive force by van der Waals force.

As a method of using a columnar fiber structure having a fine diameter as an adhesive, for example, (1) a technique in which a filter is removed after filling a filter with a columnar pore to form an adhesive, or (2) Si The technique which grows a columnar fiber structure which has a minute diameter by chemical vapor deposition (CVD method) on a board | substrate, and makes it an adhesive (patent documents 1-3) is mentioned.

However, in the technique of (1), since the filter that can be used has a limitation, there is a problem that the length of the columnar fiber structure that can be produced is not sufficient and the adhesive strength is low.

Moreover, in the technique of said (2), the adhesive force in one columnar fiber structure is high, and when converted into the adhesive force per unit area, the value equivalent to a general purpose adhesive is obtained. However, according to the adhesive evaluation method (patent document 3) of the adhesive generally performed, when the adhesive force is evaluated in the adhesive area of about 1 cm <^2> , the shear adhesive force is low and there exists a problem that it is weak compared with the conventional general purpose adhesive. .

Moreover, the characteristic calculated | required by an adhesive varies with a use. Among them, the pressure-sensitive adhesive used under high temperature conditions requires heat resistance. However, adhesives made from acrylic resins, rubber resins, styrene-butadiene copolymer resins, and the like, which are generally used general-purpose adhesives, are decomposed at a temperature of 200 ° C. or higher because the decomposition temperature of these resins is low. there is a problem. Moreover, also about the adhesive which uses materials other than the above resin as a raw material, since it carries a big change of modulus with respect to room temperature under high temperature conditions, it is inferior to the adhesive force at room temperature, and the contamination by pool residue etc. there is a problem.

Moreover, it is necessary for the adhesive which repeats adhesive peeling to a some to-be-adhered body that there is no adherend selectivity. However, adhesives made from acrylic resins, rubber resins, styrene-butadiene copolymer resins, and the like, which are generally used general-purpose adhesives, have surface freedom because the adhesive force of these resins depends on the surface free energy of the adherend. There exists a problem that adhesive force differs significantly with respect to the to-be-adhered body which energy differs greatly.

Patent Document 1: US Patent No. 6737160 Patent Document 2: US Patent Application Publication No. 2004/0071870 Patent Document 3: US Patent Application Publication No. 2006/0068195

An object of the present invention is to provide a fibrous columnar structure assembly having excellent mechanical properties, high specific surface area and excellent adhesive properties. Moreover, it is providing the fibrous columnar structure assembly which has the outstanding heat resistance, high specific surface area, and the outstanding adhesive characteristic under the temperature conditions from room temperature to high temperature. Another object of the present invention is to provide a fibrous columnar structure assembly having an adhesive property in which the adhesive force to a adherend having a high specific surface area and surface free energy does not change (no adherend selectivity). Moreover, it is providing the adhesive member using these fibrous columnar structure aggregates.

Fibrous columnar structure assembly 1 of the present invention,

A fibrous columnar structure having a plurality of diameters,

The distribution width of the diameter distribution of the fibrous columnar structure having the plurality of diameters is 10 nm or more, and the relative frequency of the mode of the diameter distribution is 30% or less.

In a preferred embodiment, the mode of the diameter distribution exists in the range of 5 nm to 15 nm.

In a preferred embodiment, the fibrous columnar structures having the plurality of diameters are oriented in the longitudinal direction.

In preferable embodiment, the shear adhesive force with respect to the glass surface at room temperature is 15 N / cm <^2> or more.

In a preferred embodiment, the fibrous columnar structure assembly 1 of the present invention further includes a base material, and one end of the fibrous columnar structure is fixed to the base material.

According to another situation of this invention, the fibrous columnar structure assembly 2 which is a carbon nanotube assembly is provided.

The fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention,

A plurality of fibrous columnar structures,

The fibrous columnar structure is a carbon nanotube, the carbon nanotube is a carbon nanotube having a plurality of layers,

The distribution width of the layer number distribution of the carbon nanotube which has this multiple layer is 10 or more layers, and the relative frequency of the mode of the layer number distribution is 25% or less.

In a preferred embodiment, the mode of the above-mentioned layer number distribution exists in the range of 2 layer number to 10 layer layer.

In a preferred embodiment, the carbon nanotubes having the plurality of layers contain carbon nanotubes having a length of 300 μm or more.

In a preferred embodiment, the carbon nanotubes having the plurality of layers are oriented in the longitudinal direction.

In preferable embodiment, the shear adhesive force with respect to the glass surface at room temperature is 15 N / cm <^2> or more.

In a preferred embodiment, the fibrous columnar structure assembly 2 of the present invention further includes a substrate, and one end of the carbon nanotube is fixed to the substrate.

According to another situation of this invention, the fibrous columnar structure assembly 3 which is a carbon nanotube assembly is provided.

The fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention,

A plurality of fibrous columnar structures,

The fibrous columnar structure is a carbon nanotube, the carbon nanotube is a carbon nanotube having a plurality of layers,

The distribution width of the layer number distribution of the carbon nanotube which has this multiple layer is 10 or more layers, the relative frequency of the mode of the layer number distribution is 25% or less,

The shear adhesive force with respect to the glass surface in 250 degreeC atmosphere is 0.8-1.2 times the shear adhesive force with respect to the glass surface at room temperature.

In a preferred embodiment, the carbon nanotubes having the plurality of layers contain carbon nanotubes having a length of 300 μm or more.

In a preferred embodiment, the mode of the above-mentioned layer number distribution exists in the range of 1 layer to 10 layer layers.

In a preferred embodiment, the carbon nanotubes having the plurality of layers are oriented in the longitudinal direction.

In preferable embodiment, the shear adhesive force with respect to the glass surface at room temperature is 15 N / cm <^2> or more.

In a preferred embodiment, the fibrous columnar structure assembly 3 of the present invention further includes a substrate, and one end of the carbon nanotube is fixed to the substrate.

According to still another aspect of the present invention, a fibrous columnar structure assembly 4 that is a carbon nanotube assembly is provided.

The fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention,

A plurality of fibrous columnar structures,

The fibrous columnar structure is a carbon nanotube, the carbon nanotube is a carbon nanotube having a plurality of layers,

The distribution width of the layer number distribution of the carbon nanotube which has this multiple layer is 10 or more layers, the relative frequency of the mode of the layer number distribution is 25% or less,

A shear adhesion force at room temperature to an adherend of surface free energy a is A, and a shear adhesion force at room temperature to an adherend of surface free energy b having a difference of 25 mJ / m ² or more from surface free energy a is B (provided that a > b), the value of B / A is 0.8-1.2.

In a preferred embodiment, the carbon nanotubes having the plurality of layers contain carbon nanotubes having a length of 300 μm or more.

In a preferred embodiment, the mode of the above-mentioned layer number distribution exists in the range of 1 layer to 10 layer layers.

In a preferred embodiment, the carbon nanotubes having the plurality of layers are oriented in the longitudinal direction.

In preferable embodiment, the shear adhesive force with respect to the glass surface at room temperature is 15 N / cm <^2> or more.

In a preferred embodiment, the fibrous columnar structure assembly 4 of the present invention further includes a substrate, and one end of the carbon nanotube is fixed to the substrate.

According to still another aspect of the present invention, an adhesive member is provided. The adhesive member of this invention uses the fibrous columnar structure assembly of this invention.

According to the present invention, it is possible to provide a fibrous columnar structure assembly having excellent mechanical properties, high specific surface area and excellent adhesive properties. Moreover, the fibrous columnar structure assembly which has the outstanding heat resistance, a high specific surface area, and the outstanding adhesive characteristic under the temperature conditions from room temperature to high temperature can be provided. In addition, it is possible to provide a fibrous columnar structure assembly having an adhesive property in which the adhesive force to a adherend having a high specific surface area and surface free energy does not change (no adherend selectivity). Moreover, the adhesive member using these fibrous columnar structure aggregates can be provided. In addition, the fibrous columnar structure assembly of the present invention is excellent in heat resistance, and thus hardly deforms even after being pressed on slide glass and placed at a high temperature of 350 ° C. for 2 hours or the like.

1 is a schematic cross-sectional view of a fibrous columnar structure assembly in a preferred embodiment of the present invention.
It is a schematic sectional drawing of the carbon nanotube aggregate manufacturing apparatus in preferable embodiment of this invention.
3 is a diagram showing the distribution of the number of layers of the carbon nanotube aggregate 1 obtained in Example 1. FIG.
4 is a diagram showing the distribution of the number of layers of the carbon nanotube aggregate 2 obtained in Example 2. FIG.
5 is a diagram showing the distribution of the number of layers of the carbon nanotube aggregate (C1) obtained in Comparative Example 1. FIG.
FIG. 6 is a diagram showing a diameter distribution of the carbon nanotube aggregate 3 obtained in Example 3. FIG.
FIG. 7 is a diagram showing a diameter distribution of the carbon nanotube aggregate 4 obtained in Example 4. FIG.
8 is a diagram showing a diameter distribution of the carbon nanotube aggregate (C2) obtained in Comparative Example 2. FIG.
9 is a diagram showing a diameter distribution of the carbon nanotube aggregate (C3) obtained in Comparative Example 3. FIG.
FIG. 10 is a diagram showing the distribution of the number of layers of the carbon nanotube aggregate 5 obtained in Example 5. FIG.
11 is a diagram showing the distribution of the number of layers of the carbon nanotube aggregate 6 obtained in Example 6. FIG.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a schematic cross sectional view of a fibrous columnar structure assembly in a preferred embodiment of the present invention (scale is not described precisely for specifying each component). The fibrous columnar structure assembly 10 includes a substrate 1 and a fibrous columnar structure 2. One end 2a of the fibrous columnar structure is fixed to the substrate 1. The fibrous columnar structure 2 is oriented in the longitudinal direction L. As shown in FIG. The fibrous columnar structure 2 is preferably oriented in a substantially vertical direction with respect to the substrate 1. Unlike the example of this figure, even when the fibrous columnar structure aggregates do not have a base material, the fibrous columnar structure aggregates may exist as aggregates by van der Waals forces, so that the fibrous columnar structure aggregates of the present invention, The aggregate which does not have a base material may be sufficient.

[Fiber columnar structure assembly 1)

The fibrous columnar structure assembly 1 of the present invention includes a fibrous columnar structure having a plurality of diameters, and the distribution width of the diameter distribution of the fibrous columnar structure having the plurality of diameters is 10 nm or more, and the diameter distribution thereof. The relative frequency of the mode of is less than 30%.

Arbitrary suitable materials can be employ | adopted as a material of the said fibrous columnar structure. For example, metals, such as aluminum and iron; Inorganic materials such as silicon; Carbon materials such as carbon nanofibers and carbon nanotubes; High modulus resins such as engineering plastics and super engineering plastics; Etc. can be mentioned. Specific examples of the resin include polyimide, polyethylene, polypropylene, polyethylene terephthalate, acetyl cellulose, polycarbonate, polyamide, and the like. Various physical properties, such as molecular weight of resin, can employ | adopt arbitrary appropriate physical properties in the range which can achieve the objective of this invention.

The distribution width of the diameter distribution of a fibrous columnar structure is 10 nm or more, Preferably it is 10-30 nm, More preferably, it is 10-25 nm, More preferably, it is 10-20 nm.

The "distribution width" of the diameter distribution of the fibrous columnar structure refers to the difference between the maximum number and the minimum number of diameters of the fibrous columnar structure. In the present invention, when the distribution width of the diameter distribution of the fibrous columnar structure is within the above range, the fibrous columnar structure can have excellent mechanical properties and high specific surface area, and the fibrous columnar structure is excellent. It may be a fibrous columnar structure assembly exhibiting adhesive properties. In addition, in this invention, what is necessary is just to measure the diameter and diameter distribution of a fibrous columnar structure with arbitrary appropriate apparatuses. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more fibrous columnar structures from the fibrous columnar aggregates may be measured by SEM or TEM to evaluate the diameter and the diameter distribution.

The maximum number of the diameters of the fibrous columnar structures is preferably 5 to 30 nm, more preferably 10 to 30 nm, still more preferably 15 to 30 nm, particularly preferably 15 to 25 nm. The minimum number of diameters of the fibrous columnar structure is preferably 1 to 15 nm, more preferably 5 to 15 nm. In the present invention, the maximum number and the minimum number of diameters of the fibrous columnar structure are within the above ranges, so that the fibrous columnar structure can have more excellent mechanical properties and higher specific surface area, and the fibrous columnar structure Can be a fibrous columnar structure assembly exhibiting even better adhesion characteristics.

The relative frequency of the mode of the diameter distribution is 30% or less, preferably 1-25%, more preferably 5-25%, still more preferably 10-25%, particularly preferably 15-25%. . In the present invention, since the relative frequency of the mode of the diameter distribution is within the above range, the fibrous columnar structure can have excellent mechanical properties and a high specific surface area, and the fibrous columnar structure exhibits excellent adhesive properties. It can be a fibrous columnar structure assembly shown.

It is preferable to exist in the range of diameter 5nm-15nm, and, as for the mode of the said diameter distribution, it is more preferable to exist in diameter 5nm-10nm. In this invention, since the mode of diameter distribution exists in the said range, the fibrous columnar structure can have the outstanding mechanical property and high specific surface area, and the fibrous columnar structure has the fibrous column which shows the outstanding adhesive characteristic. It can be a shape structure assembly.

As a shape of the said fibrous columnar structure, the cross section should just have arbitrary appropriate shapes. For example, the cross section is substantially circular, elliptical, n-square (n is an integer of 3 or more) and the like. The fibrous columnar structure may be hollow or a filling material.

The length of the fibrous columnar structure may be set to any suitable length. The length of the fibrous columnar structure is preferably 300 μm or more, more preferably 300 to 10000 μm, still more preferably 300 to 1000 μm, and particularly preferably 300 to 900 μm. In the present invention, when the length of the fibrous columnar structure is within the above range, the fibrous columnar structure can have more excellent mechanical properties and a higher specific surface area, and the fibrous columnar structure has more excellent adhesive properties. It may be a fibrous columnar structure assembly that represents.

In the fibrous columnar structure assembly 1 of the present invention, the content ratio of the fibrous columnar structure having a length of 300 µm or more in the fibrous columnar structure is preferably 80 to 100%, more preferably 90 to 100%. More preferably 95 to 100%, particularly preferably 98 to 100% and most preferably substantially 100%. Here, "substantially 100%" means 100% by the detection limit in a measuring instrument. In the present invention, the content ratio of the fibrous columnar structure having a length of 300 μm or more in the fibrous columnar structure is within the above range, so that the fibrous columnar structure can have more excellent mechanical properties and a higher specific surface area. In addition, the fibrous columnar structure can be a fibrous columnar structure assembly exhibiting even better adhesion characteristics.

As for the fibrous columnar structure assembly 1 of this invention, the shear adhesive force with respect to the glass surface at room temperature becomes like this. Preferably it is 15 N / cm <^2> or more. More preferably, it is 20-500 N / cm <^2> , More preferably, it is 30-100 N / cm <^2> , Especially preferably, it is 30-80 N / cm <^2> , Especially preferably, it is 35-50 N / cm <^2> . Here, in this invention, "room temperature" shall mean the conditions of 25 degreeC of temperature.

The specific surface area and density of the fibrous columnar structure can be set to any suitable value.

In the fibrous columnar structure assembly 1 of the present invention, when the fibrous columnar structure is a carbon nanotube, and the carbon nanotube is a carbon nanotube having a plurality of layers, the carbon nano having the plurality of layers is preferable. The distribution width of the layer number distribution of a tube is 10 or more layers, Preferably, the relative frequency of the mode of the layer number distribution is 25% or less.

The distribution width of the layer number distribution of the carbon nanotube having the plurality of layers is more preferably 10 to 30 layers, still more preferably 10 to 25 layers, and particularly preferably 10 to 20 layers.

The "distribution width" of the layer number distribution of the carbon nanotubes having the plurality of layers refers to the difference between the maximum number of layers and the minimum number of layers of the carbon nanotubes having the plurality of layers. In the present invention, the distribution width of the layer number distribution of the carbon nanotubes having a plurality of layers is within the above range, so that the carbon nanotubes can have excellent mechanical properties and high specific surface area, and the carbon nanotubes It can be a carbon nanotube aggregate exhibiting excellent adhesion properties. In addition, in this invention, what is necessary is just to measure the layer number and layer number distribution of a carbon nanotube by arbitrary appropriate apparatuses. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes from the carbon nanotube aggregate may be measured by SEM or TEM to evaluate the number of layers and the number of layer distribution.

The maximum number of layers is preferably 5 to 30 layers, more preferably 10 to 30 layers, still more preferably 15 to 30 layers, and particularly preferably 15 to 25 layers. The minimum number of layers is preferably 1 to 10 layers, more preferably 1 to 5 layers. In the present invention, the maximum number of layers and the minimum number of layers of the carbon nanotubes are within the above ranges, so that the carbon nanotubes can have more excellent mechanical properties and a higher specific surface area. It can be a carbon nanotube aggregate exhibiting excellent adhesion properties.

The relative frequency of the mode of the layer number distribution is preferably 1 to 25%, more preferably 5 to 25%, still more preferably 10 to 25%, and particularly preferably 15 to 25%. In the present invention, since the relative frequency of the mode of the layer number distribution is within the above range, the carbon nanotubes can have excellent mechanical properties and high specific surface area, and the carbon nanotubes also exhibit excellent adhesion characteristics. It can be a nano tube assembly.

The mode of the layer number distribution is preferably present in two to ten layers, and more preferably in three to ten layers. In the present invention, since the mode of the layer number distribution is within the above range, the carbon nanotubes can have both excellent mechanical properties and high specific surface area, and the carbon nanotubes can also exhibit excellent carbon nanotube aggregates. Can be

[Fiber-like columnar aggregate (2): Carbon nanotube aggregate]

The fibrous columnar structure assembly 2 which is the carbon nanotube assembly of the present invention includes a plurality of fibrous columnar structures, the fibrous columnar structure being a carbon nanotube, and the carbon nanotubes having a plurality of layers. It is a tube, the distribution width of the layer number distribution of the carbon nanotube which has this multiple layer is 10 or more layers, and the relative frequency of the mode of the layer number distribution is 25% or less.

The distribution width of the layer number distribution of the said carbon nanotube which has multiple layers is 10 or more layers, Preferably it is 10-30 layer, More preferably, it is 10-25 layer, More preferably, it is 10-20 layer.

The "distribution width" of the layer number distribution of the carbon nanotubes having the plurality of layers refers to the difference between the maximum number of layers and the minimum number of layers of the carbon nanotubes having the plurality of layers. In the present invention, the distribution width of the layer number distribution of the carbon nanotubes having a plurality of layers is within the above range, so that the carbon nanotubes can have excellent mechanical properties and high specific surface area, and the carbon nanotubes It can be a carbon nanotube aggregate exhibiting excellent adhesion properties. In addition, in this invention, what is necessary is just to measure the layer number and layer number distribution of a carbon nanotube by arbitrary appropriate apparatuses. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes from the carbon nanotube aggregate may be measured by SEM or TEM to evaluate the number of layers and the number of layer distribution.

The maximum number of layers is preferably 5 to 30 layers, more preferably 10 to 30 layers, still more preferably 15 to 30 layers, and particularly preferably 15 to 25 layers. The minimum number of layers is preferably 1 to 10 layers, more preferably 1 to 5 layers. In the present invention, the maximum number of layers and the minimum number of layers of the carbon nanotubes are within the above ranges, so that the carbon nanotubes can have more excellent mechanical properties and a higher specific surface area. It can be a carbon nanotube aggregate exhibiting excellent adhesion properties.

The relative frequency of the mode of the layer number distribution is 25% or less, preferably 1-25%, more preferably 5-25%, still more preferably 10-25%, and particularly preferably 15-25%. . In the present invention, since the relative frequency of the mode of the layer number distribution is within the above range, the carbon nanotubes can have excellent mechanical properties and high specific surface area, and the carbon nanotubes also exhibit excellent adhesion characteristics. It can be a nano tube assembly.

The mode of the layer number distribution is preferably present in two to ten layers, and more preferably in three to ten layers. In the present invention, since the mode of the layer number distribution is within the above range, the carbon nanotubes can have both excellent mechanical properties and high specific surface area, and the carbon nanotubes can also exhibit excellent carbon nanotube aggregates. Can be

As a shape of the said carbon nanotube, the cross section should just have arbitrary suitable shapes. For example, the cross section is substantially circular, elliptical, n-square (n is an integer of 3 or more) and the like.

The length of the carbon nanotubes may be set to any suitable length. The carbon nanotube having a plurality of layers, preferably contains a carbon nanotube having a length of 300 μm or more. The length of the carbon nanotube is more preferably 300 to 10000 µm, still more preferably 300 to 1000 µm, particularly preferably 300 to 900 µm. In the present invention, when the length of the carbon nanotubes is in the above range, the carbon nanotubes can have more excellent mechanical properties and a higher specific surface area, and the carbon nanotubes also have carbon which exhibits more excellent adhesion characteristics. It can be a nano tube assembly.

In the fibrous columnar structure assembly 2 which is the carbon nanotube assembly of the present invention, the content ratio of the carbon nanotubes having a length of 300 μm or more in the carbon nanotubes having the plurality of layers is preferably 80 to 100%, and more. It is preferably 90 to 100%, more preferably 95 to 100%, particularly preferably 98 to 100%, most preferably substantially 100%. Here, "substantially 100%" means 100% by the detection limit in a measuring instrument. In the fibrous columnar structure assembly 2 which is the carbon nanotube assembly of the present invention, the carbon nanotube having a content ratio of the carbon nanotube having a length of 300 μm or more in the carbon nanotube having the plurality of layers is within the above range, and thus the carbon nanotube. Can combine both excellent mechanical properties and high specific surface area, and the carbon nanotubes can be carbon nanotube aggregates which exhibit more excellent adhesion characteristics.

As for the fibrous columnar structure assembly 2 which is the carbon nanotube assembly of this invention, the shear adhesive force with respect to the glass surface at room temperature becomes like this. Preferably it is 15 N / cm <^2> or more. More preferably, it is 20-500 N / cm <^2> , More preferably, it is 30-100 N / cm <^2> , Especially preferably, it is 30-80 N / cm <^2> , Especially preferably, it is 35-50 N / cm <^2> .

The specific surface area and density of the carbon nanotubes may be set to any suitable values.

The fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention, preferably has a shear adhesion force of 0.8 to 1.2 times the shear adhesion force to the glass surface at room temperature in a 250 ° C atmosphere, and more preferably. Preferably it is 0.85 to 1.15 times, More preferably, it is 0.9 to 1.1 times. When the shear adhesion to the glass surface under a 250 ° C. atmosphere is 0.8 to 1.2 times the shear adhesion force to the glass surface at room temperature, the fibrous columnar structure assembly 2 can have excellent heat resistance, and the fibrous columnar structure assembly (2) can be a carbon nanotube aggregate exhibiting excellent adhesion characteristics under temperature conditions from room temperature to high temperature.

The fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention, preferably has a shear adhesion force to the adherend of the surface free energy a, the surface free energy of which the difference between A and the surface free energy a is 25 mJ / m ² or more. The value of B / A when the shear adhesive force used as the to-be-adhered body of b is B (where a> B) is 0.8-1.2, More preferably, it is 0.85-1.15, More preferably, it is 0.9-1.1. B / A when shear adhesion force is applied to the adherend of surface free energy a as the adherend of surface free energy b having a difference of 25 mJ / m ² or more from surface free energy a (B) (A) B When the value of is 0.8 to 1.2, the fibrous columnar structure assembly 2 is a carbon nanotube assembly having an adhesive property that does not change (adhesion selectivity) adhesion to adherends having different surface free energies. Can be.

The fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention, has a number of particles of 0.28 µm or more, preferably 30 pieces / size, remaining on the semiconductor wafer when peeled after being pressed and adhered to the semiconductor wafer. 4 inch wafers or less, more preferably 25/4 inch wafers or less, still more preferably 20/4 inch wafers or less. More specifically, 180 ° of the fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention transferred to a polypropylene resin, is pressed and bonded to a 4 inch semiconductor wafer by a 5 kg roller. When peeling with a peel, the number of particles of 0.28 micrometers or more remaining on the peeled semiconductor wafer is preferably 30 or less / 4 inch wafers, more preferably 25 or 4 inch wafers or less, further preferably Preferably less than 20/4 inch wafers. The fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention, preferably has a size of 0.28 μm remaining on the semiconductor wafer when peeling after the assembly is pressed and adhered to the semiconductor wafer as described above. Since the particle number mentioned above is a minority as mentioned above, it is very excellent in non-contamination property.

In addition, the 180 degree peel in the case of evaluating the said non-pollution property is measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece is itself a fibrous columnar structure assembly 2 (compression bonding to a semiconductor wafer), which is the carbon nanotube assembly of the present invention transferred to a polypropylene resin, and the pressing is performed by reciprocating one roller of 5 kg. It is measured at a temperature of 23 ± 2 ° C., a humidity of 65 ± 5% RH, and a peeling rate of 300 mm / min.

When the fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention, is fixed to a substrate (thickness 30 μm) of a polypropylene resin, the value of 180 ° peel is preferably 1 N / 20 mm or less, and more preferably. 0.001-1N / 20mm, More preferably, it is 0.001-0.7N / 20mm, More preferably, it is 0.001-0.5N / 20mm, Especially preferably, it is 0.001-0.4N / 20mm. The fibrous columnar structure assembly 2, which is the carbon nanotube assembly of the present invention, preferably has a 180 ° peel value when it is fixed to a substrate (thickness 30 μm) of polypropylene resin, so as to have a light peelability. Very excellent. In the case of a normal adhesive, the value of 180 degree peel is larger than 1 N / 20mm.

In addition, the 180 degree peel in the case of evaluating the said light peelability is measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece is a fibrous columnar structure assembly 2 which is a carbon nanotube assembly of the present invention transferred to a polypropylene resin having a width of 20 mm, using a silicon wafer (bare wafer, P-type, KST product) as a test plate, Squeezing is carried out by reciprocating a roller of 2 kg and measuring at a temperature of 23 ± 2 ° C., a humidity of 65 ± 5% RH, and a peeling rate of 300 mm / min.

[Fiber-like columnar aggregate (3): Carbon nanotube aggregate]

The fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention, includes a plurality of fibrous columnar structures, the fibrous columnar structures being carbon nanotubes, and the carbon nanotubes having a plurality of layers. It is a tube, the distribution width of the layer number distribution of the carbon nanotube which has this multiple layer is 10 or more layers, the relative frequency of the mode of the layer number distribution is 25% or less, and the shear adhesive force with respect to the glass surface in 250 degreeC atmosphere is room temperature. It is 0.8 ~ 1.2 times of shear adhesion force on the glass surface of.

The distribution width of the layer number distribution of the carbon nanotube having the plurality of layers is preferably 10 to 30 layers, more preferably 10 to 25 layers, still more preferably 10 to 20 layers.

The "distribution width" of the layer number distribution of the carbon nanotubes having the plurality of layers refers to the difference between the maximum number of layers and the minimum number of layers of the carbon nanotubes having the plurality of layers. In the present invention, when the distribution width of the layer number distribution of the carbon nanotube having a plurality of layers is within the above range, the carbon nanotube can have more excellent heat resistance and higher specific surface area, and the carbon nanotube May be a carbon nanotube aggregate exhibiting excellent adhesion properties under temperature conditions from room temperature to high temperature. In addition, in this invention, what is necessary is just to measure the layer number and layer number distribution of a carbon nanotube by arbitrary appropriate apparatuses. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes from the carbon nanotube aggregate may be measured by SEM or TEM to evaluate the number of layers and the number of layer distribution.

The maximum number of layers is preferably 1 to 30 layers, more preferably 1 to 25 layers, and still more preferably 2 to 25 layers. The minimum number of layers is preferably 1 to 10 layers, more preferably 1 to 5 layers. In the present invention, the maximum number of layers and the minimum number of layers of the carbon nanotubes are within the above ranges, so that the carbon nanotubes can have more excellent heat resistance and higher specific surface area, and the carbon nanotubes have room temperature. It can be a carbon nanotube aggregate exhibiting excellent adhesion characteristics under the temperature conditions up to high temperature.

The relative frequency of the mode of the layer number distribution is preferably 1 to 25%, more preferably 5 to 25%, still more preferably 10 to 25%, and particularly preferably 15 to 25%. In the present invention, since the relative frequency of the mode of the layer number distribution is within the above range, the carbon nanotubes can have more excellent heat resistance and higher specific surface area, and the carbon nanotubes can be used at room temperature to high temperature. It can be a carbon nanotube aggregate exhibiting excellent adhesion properties under temperature conditions.

The mode of distribution of the number of layers is preferably present in 1 to 10 layers, more preferably in 2 to 10 layers, and more preferably in 3 to 10 layers. . In the present invention, since the mode of the layer number distribution is within the above range, the carbon nanotubes can have more excellent heat resistance and higher specific surface area, and the carbon nanotubes can be used under temperature conditions from room temperature to high temperature. It can be a carbon nanotube aggregate exhibiting excellent adhesion properties.

As a shape of the said carbon nanotube, the cross section should just have arbitrary suitable shapes. For example, the cross section is substantially circular, elliptical, n-square (n is an integer of 3 or more) and the like.

The length of the carbon nanotubes may be set to any suitable length. The carbon nanotube having a plurality of layers, preferably contains a carbon nanotube having a length of 300 μm or more. The length of the carbon nanotube is more preferably 300 to 10000 µm, still more preferably 300 to 5000 µm, particularly preferably 300 to 2000 µm. In the present invention, when the length of the carbon nanotubes is within the above range, the carbon nanotubes can have more excellent heat resistance and higher specific surface area, and the carbon nanotubes are subjected to temperature conditions from room temperature to high temperature. It can be a carbon nanotube aggregate exhibiting excellent adhesion characteristics under the following.

In the fibrous columnar structure assembly 3 which is the carbon nanotube assembly of the present invention, the content ratio of the carbon nanotube having a length of 300 μm or more in the carbon nanotube having the plurality of layers is preferably 80 to 100%, and more. It is preferably 90 to 100%, more preferably 95 to 100%, particularly preferably 98 to 100%, most preferably substantially 100%. Here, "substantially 100%" means 100% by the detection limit in a measuring instrument. In the fibrous columnar structure assembly 3 which is the carbon nanotube assembly of the present invention, the carbon nanotube having a content ratio of the carbon nanotube having a length of 300 μm or more in the carbon nanotube having the plurality of layers is within the above range. Can have more excellent heat resistance and higher specific surface area, and the carbon nanotubes can also be carbon nanotube aggregates exhibiting excellent adhesion characteristics under temperature conditions from room temperature to high temperature.

As for the fibrous columnar structure assembly 3 which is the carbon nanotube assembly of this invention, the shear adhesive force with respect to the glass surface in 250 degreeC atmosphere is 0.8-1.2 times the shear adhesive force with respect to the glass surface at room temperature, Preferably it is 0.85-1.15. Pear, More preferably, it is 0.9-1.1 times. When the shear adhesion to the glass surface under a 250 ° C. atmosphere is 0.8 to 1.2 times the shear adhesion force to the glass surface at room temperature, the fibrous columnar structure assembly 3 can have excellent heat resistance, and the fibrous columnar structure assembly (3) can be a carbon nanotube aggregate exhibiting excellent adhesion characteristics under temperature conditions from room temperature to high temperature.

As for the fibrous columnar structure assembly 3 which is the carbon nanotube assembly of this invention, the shear adhesive force with respect to the glass surface at room temperature becomes like this. Preferably it is 15 N / cm <^2> or more. More preferably, it is 20-500 N / cm <^2> , More preferably, it is 30-100 N / cm <^2> , Especially preferably, it is 30-80 N / cm <^2> , Especially preferably, it is 35-50 N / cm <^2> .

The specific surface area and density of the carbon nanotubes may be set to any suitable values.

The fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention, preferably has a shear adhesion force to the adherend of the surface free energy a, the surface free energy of which the difference between A and the surface free energy a is 25 mJ / m ² or more. The value of B / A when the shear adhesive force used as the to-be-adhered body of b is B (where a> B) is 0.8-1.2, More preferably, it is 0.85-1.15, More preferably, it is 0.9-1.1. B / A when shear adhesion force is applied to the adherend of surface free energy a as the adherend of surface free energy b having a difference of 25 mJ / m ² or more from surface free energy a (B) (A) B When the value of is 0.8 to 1.2, the fibrous columnar structure assembly 3 is a carbon nanotube assembly having an adhesive property that does not change the adhesion force to the adherends having different surface free energy (no adherend selectivity). Can be.

The fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention, has a number of particles of 0.28 µm or more, preferably 30 pieces / size, remaining on the semiconductor wafer when peeled after being pressed and adhered to the semiconductor wafer. 4 inch wafers or less, more preferably 25/4 inch wafers or less, still more preferably 20/4 inch wafers or less. More specifically, when the fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention transferred to a polypropylene resin, is pressed and bonded to a 4 inch semiconductor wafer with a 5 kg roller, when peeled with a 180 ° peel. Of particles having a size of 0.28 μm or more remaining on the exfoliated semiconductor wafer, preferably 30/4/4 inch wafers or less, more preferably 25/4 inch wafers or less, still more preferably 20/4 inch wafers It is as follows. The fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention, preferably has a size of 0.28 µm remaining on the semiconductor wafer when the assembly is peeled after being pressed and bonded to the semiconductor wafer as described above. Since the particle number mentioned above is a minority as mentioned above, it is very excellent in non-contamination property.

In addition, the 180 degree peel in the case of evaluating the said non-pollution property is measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece is itself a fibrous columnar structure assembly 3 (compression bonding to a semiconductor wafer), which is the carbon nanotube assembly of the present invention transferred to a polypropylene resin, and the pressing is performed by reciprocating a 5 kg roller one time. It is measured at a temperature of 23 ± 2 ° C., a humidity of 65 ± 5% RH, and a peeling rate of 300 mm / min.

When the fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention, is fixed to a substrate (thickness 30 μm) of polypropylene resin, the value of 180 ° peel is preferably 1 N / 20 mm or less, and more preferably. 0.001-1N / 20mm, More preferably, it is 0.001-0.7N / 20mm, More preferably, it is 0.001-0.5N / 20mm, Especially preferably, it is 0.001-0.4N / 20mm. The fibrous columnar structure assembly 3, which is the carbon nanotube assembly of the present invention, preferably has a 180 ° peel value when it is fixed to a substrate (thickness 30 μm) of polypropylene resin as described above. Very excellent. In the case of a normal adhesive, the value of 180 degree peel is larger than 1 N / 20mm.

In addition, the 180 degree peel in the case of evaluating the said light peelability is measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece is a fibrous columnar structure assembly 3 which is a carbon nanotube assembly of the present invention transferred to a polypropylene resin having a width of 20 mm, using a silicon wafer (bare wafer, P type, KST product) as a test plate, Squeezing is carried out by reciprocating a roller of 2 kg and measuring at a temperature of 23 ± 2 ° C., a humidity of 65 ± 5% RH, and a peeling rate of 300 mm / min.

[Fiber-like columnar aggregate (4): carbon nanotube aggregate]

The fibrous columnar structure assembly 4 which is the carbon nanotube assembly of the present invention includes a plurality of fibrous columnar structures, the fibrous columnar structure being a carbon nanotube, and the carbon nanotubes having a plurality of layers. It is a tube, the distribution width of the layer number distribution of the carbon nanotube which has this multiple layer is 10 or more layers, the relative frequency of the mode of the layer number distribution is 25% or less, and the shear at room temperature with respect to the to-be-adhered body of surface free energy a. When the adhesive force is A and the shear adhesion force at room temperature to the adherend of surface free energy b having a difference of 25 mJ / m ² or more from surface free energy a is B (where a> b), the value of B / A is 0.8 to 1.2. to be.

The distribution width of the layer number distribution of the carbon nanotube having the plurality of layers is preferably 10 to 30 layers, more preferably 10 to 25 layers, still more preferably 10 to 20 layers.

The "distribution width" of the layer number distribution of the carbon nanotubes having the plurality of layers refers to the difference between the maximum number of layers and the minimum number of layers of the carbon nanotubes having the plurality of layers. In the present invention, the distribution width of the number distribution of the carbon nanotubes having a plurality of layers is within the above range, so that the carbon nanotubes can have a higher specific surface area, and the carbon nanotubes have a surface free energy. It can be a carbon nanotube aggregate having adhesive properties in which adhesion to different adherends does not change (no adherend selectivity). In addition, in this invention, what is necessary is just to measure the layer number and layer number distribution of a carbon nanotube by arbitrary appropriate apparatuses. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes from the carbon nanotube aggregate may be measured by SEM or TEM to evaluate the number of layers and the number of layer distribution.

The maximum number of layers is preferably 1 to 30 layers, more preferably 1 to 25 layers, and still more preferably 2 to 25 layers. The minimum number of layers is preferably 1 to 10 layers, more preferably 1 to 5 layers. In the present invention, the maximum number of layers and the minimum number of layers of the carbon nanotubes are within the above ranges, so that the carbon nanotubes can have a higher specific surface area, and the carbon nanotubes have different surface free energies. It can be a carbon nanotube aggregate having adhesive properties in which the adhesion to the complex does not change (there is no adherend selectivity).

The relative frequency of the mode of the layer number distribution is preferably 1 to 25%, more preferably 5 to 25%, still more preferably 10 to 25%, and particularly preferably 15 to 25%. In the present invention, since the relative frequency of the mode of the layer number distribution is within the above range, the carbon nanotubes can have a higher specific surface area, and the carbon nanotubes have adhesion to adherends having different surface free energies. This can be a carbon nanotube aggregate having an adhesive property that does not change (no adherend selectivity).

The mode of distribution of the number of layers is preferably present in 1 to 10 layers, more preferably in 2 to 10 layers, and more preferably in 3 to 10 layers. . In the present invention, since the mode of the layer number distribution is within the above range, the carbon nanotubes can have a higher specific surface area, and the carbon nanotubes do not change the adhesion to adherends having different surface free energies. Carbon nanotube aggregates having non-adhesive selectivity.

As a shape of the said carbon nanotube, the cross section should just have arbitrary suitable shapes. For example, the cross section is substantially circular, elliptical, n-square (n is an integer of 3 or more) and the like.

* The length of the carbon nanotube can be set to any suitable length. The carbon nanotube having a plurality of layers, preferably contains a carbon nanotube having a length of 300 μm or more. The length of the carbon nanotube is more preferably 300 to 10000 µm, still more preferably 300 to 5000 µm, particularly preferably 300 to 2000 µm. In the present invention, since the length of the carbon nanotubes is within the above range, the carbon nanotubes can have a higher specific surface area, and the carbon nanotubes have a change in adhesion to adherends having different surface free energies. Carbon nanotube aggregates having non-adhesive (no adherend selectivity) properties.

In the fibrous columnar structure assembly 4 which is the carbon nanotube assembly of the present invention, the content ratio of the carbon nanotube having a length of 300 μm or more in the carbon nanotube having the plurality of layers is preferably 80 to 100%, and more. It is preferably 90 to 100%, more preferably 95 to 100%, particularly preferably 98 to 100%, most preferably substantially 100%. Here, "substantially 100%" means 100% by the detection limit in a measuring instrument. In the fibrous columnar structure assembly 4 which is the carbon nanotube aggregate of the present invention, the carbon nanotube having a content ratio of the carbon nanotube having a length of 300 μm or more in the carbon nanotube having the plurality of layers is within the above range, and thus the carbon nanotube. Can have a higher specific surface area, and the carbon nanotubes can be carbon nanotube assemblies having adhesive properties in which adhesion to surfaces having different surface free energies does not change (no adherend selectivity). .

As for the fibrous columnar structure assembly 4 which is the carbon nanotube assembly of this invention, the shear adhesive force with respect to the glass surface at room temperature becomes like this. Preferably it is 15 N / cm <^2> or more. More preferably, it is 20-500 N / cm <^2> , More preferably, it is 30-100 N / cm <^2> , Especially preferably, it is 30-80 N / cm <^2> , Especially preferably, it is 35-50 N / cm <^2> .

The fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention, has a shear adhesion force at room temperature to an adherend of surface free energy a, and a surface free energy b having a difference of 25 mJ / m ² or more from the surface free energy a. When the shear adhesive force at room temperature to the adherend of B is B (where a> b), the value of B / A is 0.8 to 1.2, preferably 0.85 to 1.15, and more preferably 0.9 to 1.1. When shear adhesion force at room temperature to the adherend of surface free energy a is A and shear adhesion force at room temperature to the adherend of surface free energy b having a difference of 25 mJ / m ² or more from surface free energy a as B ( Since the value of B / A of a> b) is 0.8-1.2, the fibrous columnar structure assembly 4 has the adhesive force which does not change (no adherend selectivity) with respect to the to-be-adhered body from which surface free energy differs. It can be a carbon nanotube aggregate having characteristics.

The specific surface area and density of the carbon nanotubes may be set to any suitable values.

The fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention, preferably has a shear adhesion force of 0.8 to 1.2 times the shear adhesion force to the glass surface at room temperature in a 250 ° C atmosphere, and more preferably. Preferably it is 0.85 to 1.15 times, More preferably, it is 0.9 to 1.1 times. When the shear adhesion to the glass surface under a 250 ° C. atmosphere is 0.8 to 1.2 times the shear adhesion force to the glass surface at room temperature, the fibrous columnar structure assembly 4 can have excellent heat resistance, and the fibrous columnar structure assembly (4) can be a carbon nanotube aggregate exhibiting excellent adhesion characteristics under temperature conditions from room temperature to high temperature.

The fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention, has a number of particles of 0.28 µm or more, preferably 30 pieces / size, remaining on the semiconductor wafer when peeled after being pressed and adhered to the semiconductor wafer. 4 inch wafers or less, more preferably 25/4 inch wafers or less, still more preferably 20/4 inch wafers or less. More specifically, when the fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention transferred to a polypropylene resin, is pressed and bonded to a 4 inch semiconductor wafer by a 5 kg roller, when peeled with a 180 ° peel. Of particles having a size of 0.28 μm or more remaining on the exfoliated semiconductor wafer, preferably 30/4/4 inch wafers or less, more preferably 25/4 inch wafers or less, still more preferably 20/4 inch wafers It is as follows. The fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention, preferably has a size of 0.28 μm remaining on the semiconductor wafer when the assembly is peeled after being pressed and bonded to the semiconductor wafer as described above. Since the particle number mentioned above is a minority as mentioned above, it is very excellent in non-contamination property.

In addition, the 180 degree peel in the case of evaluating the said non-pollution property is measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece is itself a fibrous columnar structure assembly 4 (compression bonding to a semiconductor wafer), which is the carbon nanotube assembly of the present invention transferred to a polypropylene resin, and the crimping is performed by reciprocating one roller of 5 kg. It is measured at a temperature of 23 ± 2 ° C., a humidity of 65 ± 5% RH, and a peeling rate of 300 mm / min.

When the fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention, is fixed to a substrate (thickness 30 μm) of polypropylene resin, the value of the 180 ° peel is preferably 1 N / 20 mm or less, and more preferably. 0.001-1N / 20mm, More preferably, it is 0.001-0.7N / 20mm, More preferably, it is 0.001-0.5N / 20mm, Especially preferably, it is 0.001-0.4N / 20mm. The fibrous columnar structure assembly 4, which is the carbon nanotube assembly of the present invention, preferably has a 180 ° peel value when it is fixed to a substrate (thickness 30 μm) of a polypropylene resin, so as to have a light peelability. Very excellent. In the case of a normal adhesive, the value of 180 degree peel is larger than 1 N / 20mm.

In addition, the 180 degree peel in the case of evaluating the said light peelability is measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece is a fibrous columnar structure assembly 4 which is a carbon nanotube assembly of the present invention transferred to a polypropylene resin having a width of 20 mm, using a silicon wafer (bare wafer, P-type, KST product) as a test plate, Squeezing is carried out by reciprocating a roller of 2 kg and measuring at a temperature of 23 ± 2 ° C., a humidity of 65 ± 5% RH, and a peeling rate of 300 mm / min.

[Method for producing fibrous columnar structure assembly]

Arbitrary suitable methods can be employ | adopted as a manufacturing method of the fibrous columnar structure assembly of this invention. As an example of the preferable embodiment of the manufacturing method of the fibrous columnar structure assembly of this invention, the manufacturing method of the fibrous columnar structure assembly which is a carbon nanotube assembly is demonstrated.

Arbitrary appropriate methods can be employ | adopted as a manufacturing method of the fibrous columnar structure assembly which is the carbon nanotube assembly of this invention. For example, by chemical vapor deposition (CVD), a catalyst layer is formed on a smooth substrate, a carbon source is charged in a state where the catalyst is activated by heat, plasma, or the like, and the carbon nanotubes are grown. And a method of producing a carbon nanotube assembly oriented almost vertically from a substrate. In this case, if the substrate is removed, the carbon nanotube aggregate oriented in the longitudinal direction can be obtained.

Arbitrary appropriate board | substrates can be employ | adopted as the said board | substrate. For example, the material which has smoothness and has high temperature heat resistance which can endure manufacture of a carbon nanotube is mentioned. As such a material, metal plates, such as quartz glass, silicon (silicon wafer, etc.), aluminum, etc. are mentioned, for example.

Arbitrary suitable apparatus can be employ | adopted as an apparatus for manufacturing the fibrous columnar structure assembly which is the carbon nanotube assembly of this invention. For example, as a thermal CVD apparatus, the hot-wall type etc. which comprised the cylindrical reaction container enclosed by the resistance heating type electric tubular furnace as shown in FIG. 2 are mentioned. In that case, as a reaction container, a heat resistant quartz tube etc. are used preferably, for example.

Arbitrary suitable catalysts can be used as a catalyst (material of a catalyst layer) which can be used for manufacture of the fibrous columnar structure assembly which is the carbon nanotube aggregate of this invention. For example, metal catalysts, such as iron, cobalt, nickel, gold, platinum, silver, copper, are mentioned.

When manufacturing the fibrous columnar structure aggregate which is the carbon nanotube aggregate of this invention, you may provide an alumina / hydrophilic film between a board | substrate and a catalyst layer as needed.

Arbitrary appropriate methods can be employ | adopted as a manufacturing method of an alumina / hydrophilic film. For example, a SiO ₂ film is formed on a substrate, Al is deposited, and then, the temperature is raised to 450 ° C. and oxidized. According to this production method, Al ₂ O ₃ is to interact with the hydrophilic SiO ₂ film, Al these different Al ₂ O ₃ side than the particle diameter will directly deposit the ₂ O ₃ is formed. Even if Al is deposited and then the temperature is raised to 450 ° C. without producing a hydrophilic film on the substrate, there is a possibility that Al ₂ O ₃ faces having different particle diameters may not be formed. Further, making the substrate, a hydrophilic film and may be directly depositing Al ₂ O _3, there is a fear difficult to particle size of different Al ₂ O ₃ surface is formed.

In order to form microparticles | fine-particles, the thickness of the catalyst layer which can be used for manufacture of the fibrous columnar structure assembly which is the carbon nanotube aggregate of this invention becomes like this. Preferably it is 0.01-20 nm, More preferably, it is 0.1-10 nm. Since the thickness of the catalyst layer which can be used to manufacture the fibrous columnar structure aggregate which is the carbon nanotube aggregate of the present invention is within the above range, the fibrous columnar structure can have excellent mechanical properties and high specific surface area, and The fibrous columnar structure can be a fibrous columnar structure assembly exhibiting excellent adhesive properties. Arbitrary appropriate methods can be employ | adopted for the formation method of a catalyst layer. For example, the method of depositing a metal catalyst by EB (electron beam), a sputter | spatter, etc., the method of apply | coating the suspension of metal catalyst fine particles on a board | substrate, etc. are mentioned.

Arbitrary suitable carbon sources can be used as a carbon source which can be used for manufacture of the fibrous columnar structure assembly which is the carbon nanotube assembly of this invention. For example, hydrocarbons, such as methane, ethylene, acetylene, benzene; Alcohols such as methanol and ethanol; Etc. can be mentioned.

Arbitrary appropriate temperatures can be employ | adopted as manufacture temperature in manufacture of the fibrous columnar structure assembly which is the carbon nanotube aggregate of this invention. For example, in order to form the catalyst particle which can fully express the effect of this invention, Preferably it is 400-1000 degreeC, More preferably, it is 500-900 degreeC, More preferably, it is 600-800 degreeC.

[Adhesion member]

The adhesive member of this invention uses the fibrous columnar structure assembly of this invention. As for the adhesive member of this invention, Preferably, the fibrous columnar structure assembly of this invention is equipped with a base material, Specifically, an adhesive sheet and an adhesive film are mentioned, for example.

As a base material of an adhesion member, quartz glass, silicon (silicon wafer etc.), an engineering plastic, a super engineering plastic, etc. are mentioned. Specific examples of the engineering plastics and the super engineering plastics include polyimide, polyethylene, polyethylene terephthalate, acetyl cellulose, polycarbonate, polypropylene, and polyamide. Various physical properties, such as molecular weight, can employ | adopt arbitrary appropriate physical properties in the range which can achieve the objective of this invention.

The thickness of the substrate can be set to any suitable value, depending on the purpose. For example, in the case of a silicon substrate, Preferably it is 100-10000 micrometers, More preferably, it is 100-5000 micrometers, More preferably, it is 100-2000 micrometers. For example, in the case of a polypropylene board | substrate, Preferably it is 1-1000 micrometers, More preferably, it is 1-500 micrometers, More preferably, it is 5-100 micrometers.

The surface of the substrate is chemically treated such as conventional surface treatment, for example, chromic acid treatment, ozone exposure, flame exposure, high pressure electric shock exposure, ionization radiation treatment, etc. in order to improve the adhesion to the adjacent layers, the retention properties, and the like. Alternatively, a physical treatment or a coating treatment with a primer (for example, the adhesive substance) may be performed.

A single layer may be sufficient as the said base material, and a multilayer body may be sufficient as it.

When fixing the fibrous columnar structural body assembly of this invention to a base material, arbitrary appropriate methods can be employ | adopted as the method. For example, you may use the board | substrate used for manufacture of a fibrous columnar structure as a base material as it is. Moreover, you may provide and fix an adhesive layer to a base material. In addition, when a base material is a thermosetting resin, a thin film is produced in the state before reaction, one end of a carbon nanotube is crimped | bonded to a thin film layer, and what is necessary is just to perform a hardening process and fix it. Moreover, when a base material is a thermoplastic resin, a metal, etc., after crimping | bonding one end of a fibrous columnar structure in a molten state, what is necessary is just to cool and fix to room temperature.

<Examples>

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these. Moreover, evaluation of the diameter and diameter distribution of a fibrous columnar structure in a fibrous columnar structure assembly, evaluation of the layer number and layer number distribution of a fibrous columnar structure in a fibrous columnar structure assembly, and the shear adhesive force of the fibrous columnar structure assembly The measurement and the evaluation of the surface free energy of the adherend were performed by the following method.

<Evaluation of Diameter and Diameter Distribution of Fibrous Columnar Structures in Fibrous Columnar Structures>

The diameter and diameter distribution of the fibrous columnar structure in the fibrous columnar assembly of the present invention were measured by a scanning electron microscope (SEM) and / or a transmission electron microscope (TEM). At least 10 or more, preferably 20 or more fibrous columnar structures of the obtained fibrous columnar aggregates were observed by SEM and / or TEM, and the diameters of the respective fibrous columnar structures were examined to prepare a diameter distribution.

<Evaluation of Layer Number and Layer Number Distribution of Fibrous Columnar Structures in Fibrous Columnar Structures>

The number of layers and the number of layer distribution of the fibrous columnar structure in the fibrous columnar structure assembly of the present invention were measured by a scanning electron microscope (SEM) and / or a transmission electron microscope (TEM). At least 10 or more, preferably 20 or more fibrous columnar structures of the obtained fibrous columnar aggregates were observed by SEM and / or TEM, and the number of layers of each fibrous columnar structure was investigated to create a layer number distribution.

<Measurement Method (A) of Shear Adhesion of Fibrous Columnar Structures>

On the glass (MATSUNAMI slide glass 27 mm x 56 mm), the tip of the fibrous columnar structure assembly with the base material cut out in 1 cm ² unit area was placed in contact with each other. A 5 kg roller was reciprocated to press the tip of the fibrous columnar structure to the glass. . Thereafter, it was left to stand for 30 minutes. A shear test was performed at 25 ° C or 250 ° C at a tensile speed of 50 mm / min with a tensile tester (Instro Tensil Tester), and the resulting peak was defined as shear adhesion.

<Measurement Method (B) of Shear Adhesion of Fibrous Columnar Structures>

Glass (MATSUNAMI slide glass 27mm × 56mm, surface free energy = 64.4mJ / m ² ) and PP plate (made by Shin-Kobe Electric Co., Ltd., Kobe polysheet PP-N-AN, surface free energy = 29.8mJ / m ² ) To each of them, the tip of the carbon nanotube aggregate with the substrate cut out in 1 cm ² unit area was placed in contact with each other, and a 5 kg roller was reciprocated to press the tip of the carbon nanotube onto the glass. Thereafter, it was left to stand for 30 minutes. A shear test was carried out at 25 ° C. at a tensile rate of 50 mm / min with a tensile tester (Instro Tensil Tester), and the resulting peak was defined as shear adhesion.

<Evaluation of surface free energy of adherend>

After dropping three liquids (water, glycerin, methylene iodide) on the surface of the adherend, a contact angle of 100 ms was measured, and the surface free energy was obtained from the following method using the value.

Calculation method of surface free energy:

_{γ L (1 + cosθ) =} 2 (γ L d · γ s d) 1/2 +2 (γ L p · γ s p) 1/2 ··· (1)

γ _L : surface free energy of liquid used for contact angle measurement

γ _L ^d : dispersion component of surface free energy of liquid

γ _L ^p : Polar component of surface free energy of liquid

γ _s : surface free energy of solid

γ _s ^d : dispersion component of surface free energy of solid

γ _s ^p : Polar component of surface free energy of solid

Equation (1) is transformed into a linear function of (γ _L ^p / γ _L ^d ) ^1/2 and γ _L (1 + cosθ) / 2 (γ _L ^d ) ^1/2 ,

γ _L (1 + cosθ) / 2 (γ _L ^d ) ^1/2

(γ _s ^p ) ^1/2 (γ _L ^p / γ _L ^d ) ^1/2 + (γ _s ^d ) ^1/2

From equation (2), γ _s ^d and γ _s ^p were obtained by multiplying [tilt] by the power of 2 and [intercept], respectively, and calculating surface free energy as γ _s = γ _s ^d + γ _s ^p .

Example 1

(Production of Carbon Nanotube Aggregates)

Vacuum vapor deposition apparatus (JEEOL, JEE-4X) on a silicon substrate having a SiO ₂ film on its surface (a wafer having a thermal oxide film, a KST material, a SiO ₂ film thickness = 1 μm, and a thickness of a SiO ₂ film and a silicon substrate = 550 μm). After the Al thin film (thickness 10 nm) was formed by a vacuum evaporator, oxidation treatment was performed at 450 ° C. for 1 hour. In this way, an Al ₂ O ₃ film was formed on the silicon substrate. On this Al ₂ O ₃ film, a thin Fe film (thickness 2 nm) was deposited by a sputtering device (manufactured by ULVAC, RFS-200) to further form a catalyst layer.

Next, the silicon substrate having a catalyst layer was cut, placed in a 30 mm phi quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm was allowed to flow through the quartz tube for 30 minutes, thereby replacing the inside of the tube. Thereafter, the tube was gradually heated up to 765 ° C for 35 minutes using an electric tube furnace, and stabilized at 765 ° C. After standing at 765 ° C. for 10 minutes, helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) mixed gas was charged into the tube while the temperature was maintained, and left for 30 minutes to grow carbon nanotubes on the substrate. To obtain a carbon nanotube aggregate (1).

The carbon nanotube aggregate 1 was 638 µm in length.

The layer number distribution of the carbon nanotube aggregate 1 is shown in FIG. 3. As shown in FIG. 3, the mode existed in 4th floor and 8th floor, and the relative frequency was 20%, respectively.

Moreover, the distribution width of the diameter distribution of the carbon nanotube aggregate 1, the mode of diameter distribution, and the relative frequency of the mode were also measured.

The results are summarized in Table 1.

(Measurement of Shear Adhesion)

The polypropylene resin (30 micrometers in thickness made by Asahi Yangji Pulp Co., Ltd.) was heated at 200 degreeC on the hotplate, and was melted. One end (upper end) of the carbon nanotubes formed by vertically aligning the substrate was pressed onto a molten polypropylene resin, and then cooled to room temperature and fixed. Thus, the carbon nanotube aggregate (1) with a base material was obtained.

Using the carbon nanotube aggregate (1) with a substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 44.6 N / cm ² .

The results are summarized in Table 1.

[Example 2]

Carbon nanotubes were prepared in the same manner as in Example 1 except that a mixed gas of helium / hydrogen / ethylene (105/80 / 15sccm, moisture content 350ppm) was charged into a quartz tube and left for 20 minutes to grow a carbon nanotube on a substrate. The tube assembly 2 was produced.

The carbon nanotube aggregate 2 had a length of 420 µm.

The layer number distribution of the carbon nanotube aggregate 2 is shown in FIG. 4. As shown in FIG. 4, the mode existed in the 9th floor and the relative frequency was 20%.

Moreover, the distribution width of the diameter distribution of the carbon nanotube aggregate 2, the mode of diameter distribution, and the relative frequency of the mode were also measured.

In the same manner as in Example 1, a carbon nanotube aggregate (2) with a substrate was obtained.

Using the carbon nanotube aggregate (2) with a substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 36.1 N / cm ² .

The results are summarized in Table 1.

Comparative Example 1

(Production of Carbon Nanotube Aggregates)

After forming an Al thin film (thickness of 10 nm) by a vacuum evaporation apparatus (JEEOL, JEE-4X Vacuum Evaporator) on a silicon substrate (electronic end agent, thickness 525 micrometers), it oxidizes at 450 degreeC for 1 hour. did. In this way, an Al ₂ O ₃ film was formed on the silicon substrate. On this Al ₂ O ₃ film, a thin Fe film (thickness 0.67 nm) was deposited by a sputtering device (manufactured by ULVAC, RFS-200) to further form a catalyst layer.

Next, the silicon substrate having a catalyst layer was cut, placed in a 30 mm phi quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm was allowed to flow through the quartz tube for 30 minutes, thereby replacing the inside of the tube. Thereafter, the tube was gradually heated up to 765 ° C for 35 minutes using an electric tube furnace, and stabilized at 765 ° C. After standing at 765 ° C. for 10 minutes, helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) mixed gas was charged into the tube while the temperature was maintained, and left for 30 minutes to grow carbon nanotubes on the substrate. To obtain a carbon nanotube aggregate (C1).

The length of the carbon nanotube aggregate (C1) was 799 μm.

The layer number distribution of the carbon nanotube aggregate (C1) is shown in FIG. 5. As shown in FIG. 5, the mode existed in the 4th floor and the relative frequency was 27%.

Moreover, the distribution width of the diameter distribution of the carbon nanotube aggregate (C1), the mode of diameter distribution, and the relative frequency of the mode were also measured.

The results are summarized in Table 1.

(Measurement of Shear Adhesion)

The polypropylene resin (30 micrometers in thickness made by Asahi Yangji Pulp Co., Ltd.) was heated at 200 degreeC on the hotplate, and was melted. One end (upper end) of the carbon nanotubes formed by vertically aligning the substrate was pressed onto a molten polypropylene resin, and then cooled to room temperature and fixed. Thus, the carbon nanotube aggregate (C1) with a base material was obtained.

Using the carbon nanotube aggregate (C1) with a substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 7.9 N / cm ² .

The results are summarized in Table 1.

As shown in Examples 1 and 2, when the layer number distribution of the carbon nanotubes, which are fibrous columnar structures, is dispersed and the relative frequency of the mode of the layer number distribution is 25% or less, the shear adhesion to the glass surface is 30 N / cm ² or more. The value was shown. On the contrary, as shown in Comparative Example 1, when the layer number distribution of the carbon nanotube which is a fibrous columnar structure was monodispersed and the relative frequency of the mode of the layer number distribution was more than 25%, the shear adhesive force was 10 N / cm ^2. Low values were shown.

In Examples 1 and 2, as a mechanism which can express high shear adhesive force, it can think as follows. Carbon nanotubes having a small number of layers follow the surface irregularities of the glass, and the contact area is increased, resulting in strong adhesion. However, the carbon nanotubes may not be able to follow the surface irregularities of the glass due to the aggregation of the carbon nanotubes. On the other hand, carbon nanotubes having a large number of layers have a low trackability against the surface irregularities of the glass, whereas the carbon nanotubes do not have agglomeration of the carbon nanotubes, so that the decrease in adhesion force is small. In Examples 1 and 2, carbon nanotubes having a small number of layers and carbon nanotubes having a large number of layers exist in a wide distribution, thereby preventing agglomeration of the carbon nanotubes, so that the carbon nanotubes act independently of each other. It can be considered that following the unevenness, the adhesive area increases, and the strong adhesion is expressed.

In Examples 1 and 2, the cause of broadening the distribution of the carbon nanotubes can be considered as follows. Regarding the carbon nanotubes, it is thought that the Fe deposition film is thicker than the conventional one, which partially prevents the formation of fine particles at high temperature and broadens the distribution of the Fe particle diameter. In addition, even if the thickness of the conventional Fe-deposited film is used, it can be considered that by using a Si substrate having an SiO ₂ oxide film, the distribution of the surface irregularities of Al ₂ O ₃ is broadened to affect the diameter distribution of the Fe fine particles.

Example 3

(Production of Carbon Nanotube Aggregates)

Vacuum vapor deposition apparatus (JEEOL, JEE-4X) on a silicon substrate having a SiO ₂ film on its surface (a wafer having a thermal oxide film, a KST material, a SiO ₂ film thickness = 1 μm, and a thickness of a SiO ₂ film and a silicon substrate = 550 μm). After the Al thin film (thickness 10 nm) was formed by a vacuum evaporator, oxidation treatment was performed at 450 ° C. for 1 hour. In this way, an Al ₂ O ₃ film was formed on the silicon substrate. On this Al ₂ O ₃ film, a thin Fe film (thickness 2 nm) was deposited by a sputtering device (manufactured by ULVAC, RFS-200) to further form a catalyst layer.

Next, the silicon substrate having a catalyst layer was cut, placed in a 30 mm phi quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm was allowed to flow through the quartz tube for 30 minutes, thereby replacing the inside of the tube. Then, the inside of a pipe | tube was heated up gradually to 700 degreeC for 30 minutes using the electric tubular furnace, and it stabilized at 700 degreeC. After standing at 700 ° C. for 10 minutes, helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) mixed gas was charged into the tube while the temperature was maintained, and left for 30 minutes to grow carbon nanotubes on the substrate. To obtain a carbon nanotube aggregate (3).

The carbon nanotube aggregate 3 had a length of 722 µm.

The diameter distribution of the carbon nanotube aggregate 3 is shown in FIG. As shown in FIG. 6, the mode existed at 12 nm and the relative frequency was 25%.

Moreover, the distribution width of the layer number distribution of the carbon nanotube aggregate 3, the mode of the layer number distribution, and the relative frequency of the mode were also measured.

The results are summarized in Table 2.

(Measurement of Shear Adhesion)

The polypropylene resin (30 micrometers in thickness made by Asahi Yangji Pulp Co., Ltd.) was heated at 200 degreeC on the hotplate, and was melted. One end (upper end) of the carbon nanotubes formed by vertically aligning the substrate was pressed onto a molten polypropylene resin, and then cooled to room temperature and fixed. Thus, the carbon nanotube aggregate (3) with a base material was obtained.

Using the carbon nanotube aggregate (3) with the substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 40.5 N / cm ² .

The results are summarized in Table 2.

Example 4

Carbon nanotubes were prepared in the same manner as in Example 3, except that a mixed gas of helium / hydrogen / ethylene (105/80 / 15sccm, moisture content 350ppm) was charged into a quartz tube and allowed to stand for 20 minutes to grow a carbon nanotube on a substrate. The tube assembly 4 was produced.

The carbon nanotube aggregate 4 had a length of 570 µm.

The diameter distribution of the carbon nanotube aggregate 4 is shown in FIG. As shown in FIG. 7, the mode existed at 13 nm and the relative frequency was 22.2%.

Moreover, the distribution width of the layer number distribution of the carbon nanotube aggregate 4, the mode of the layer number distribution, and the relative frequency of the mode were also measured.

In the same manner as in Example 3, a carbon nanotube aggregate (4) with a substrate was obtained.

Using the carbon nanotube aggregate (4) with a substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 31.2 N / cm ² .

The results are summarized in Table 2.

Comparative Example 2

(Production of Carbon Nanotube Aggregates)

After forming an Al thin film (thickness of 10 nm) by a vacuum evaporation apparatus (JEEOL, JEE-4X Vacuum Evaporator) on a silicon substrate (electronic end agent, thickness 525 micrometers), it oxidizes at 450 degreeC for 1 hour. did. In this way, an Al ₂ O ₃ film was formed on the silicon substrate. On this Al ₂ O ₃ film, a thin Fe film (thickness 0.67 nm) was deposited by a sputtering device (manufactured by ULVAC, RFS-200) to further form a catalyst layer.

Next, the silicon substrate having a catalyst layer was cut, placed in a 30 mm phi quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm was allowed to flow in the quartz tube for 20 minutes to replace the tube. Then, the inside of a pipe | tube was heated up gradually to 700 degreeC for 30 minutes using the electric tubular furnace, and it stabilized at 700 degreeC. After standing at 700 ° C. for 10 minutes, helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) mixed gas was charged into the tube while the temperature was maintained, and left for 20 minutes to grow carbon nanotubes on the substrate. To obtain a carbon nanotube aggregate (C2).

The length of the carbon nanotube aggregate (C2) was 589 μm.

The diameter distribution of carbon nanotube aggregate (C2) is shown in FIG. As shown in FIG. 8, the mode existed at 5 nm and the relative frequency was 85.7%.

Moreover, the distribution width of the layer number distribution of the carbon nanotube aggregate (C2), the mode of the layer number distribution, and the relative frequency of the mode were also measured.

The results are summarized in Table 2.

(Measurement of Shear Adhesion)

The polypropylene resin (30 micrometers in thickness made by Asahi Yangji Pulp Co., Ltd.) was heated at 200 degreeC on the hotplate, and was melted. One end (upper end) of the carbon nanotubes formed by vertically aligning the substrate was pressed onto a molten polypropylene resin, and then cooled to room temperature and fixed. Thus, the carbon nanotube aggregate (C2) with a base material was obtained.

Using the carbon nanotube aggregate (C2) with a substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 15.3 N / cm ² .

The results are summarized in Table 2.

Comparative Example 3

Carbon nanotubes were prepared in the same manner as in Comparative Example 2 except that a mixed gas of helium / hydrogen / ethylene (105/80 / 15sccm, moisture content 350ppm) was charged into a quartz tube and left to stand for 10 minutes to grow a carbon nanotube on a substrate. The tube assembly C3 was produced.

The carbon nanotube aggregate (C3) was 630 µm in length.

The diameter distribution of the carbon nanotube aggregate (C3) is shown in FIG. As shown in FIG. 9, the mode existed in 13 nm and the relative frequency was 40%.

Moreover, the distribution width of the layer number distribution of the carbon nanotube aggregate (C3), the mode of the layer number distribution, and the relative frequency of the mode were also measured.

In the same manner as in Comparative Example 2, a carbon nanotube aggregate (C3) with a substrate was obtained.

Using the carbon nanotube aggregate (C3) with a substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 11.5 N / cm ² .

The results are summarized in Table 2.

As shown in Examples 3 and 4, when the diameter distribution of the carbon nanotube which is a fibrous columnar structure is dispersed, and the relative frequency of the mode of the diameter distribution is 30% or less, the shear adhesion force to the glass surface is 30 N / cm ² or more. The value was shown. On the contrary, as shown in Comparative Example 2, when the diameter distribution of the carbon nanotube which is a fibrous columnar structure is monodispersed and the relative frequency of the mode of the diameter distribution exceeds 30%, As described above, even if the mode of the diameter distribution of the carbon nanotube which is a fibrous columnar structure is in the range of 5 nm to 15 nm, when the relative frequency of the mode of the diameter distribution exceeds 30%, the low value that the shear adhesive force is less than 20 N / cm ^2. Indicated.

In Examples 3 and 4, as a mechanism capable of expressing high shear adhesion, it can be considered as follows. The small diameter fibrous columnar structure follows the surface irregularities of the glass, and the contact area is increased, resulting in strong adhesion, while the fibrous columnar structures may not be able to follow the glass surface irregularities due to the aggregation of the fibrous columnar structures. On the other hand, the fibrous columnar structure having a large diameter has low trackability to the surface irregularities of the glass, while the cohesion of the fibrous columnar structures is not agglomerated, so that the decrease in adhesion force is small. In Examples 3 and 4, the fibrous columnar structure having a small diameter and the fibrous columnar structure having a large diameter are present in a wide distribution, thereby preventing the aggregation of the fibrous columnar structures, so that each of the fibrous columnar structures acts independently. It can be considered that, following the surface irregularities of the glass, the adhesion area increases to express the strong adhesion.

In addition, in Example 3, 4, it can think as follows as a cause of broadening distribution of a fibrous columnar structure. Regarding the fibrous columnar structure, it is considered that the Fe deposition film is made thicker than the conventional one, which partially prevents the formation of fine particles at high temperature and broadens the distribution of the Fe particle diameter. In addition, even if the thickness of the conventional Fe-deposited film is used, it can be considered that by using a Si substrate having an SiO ₂ oxide film, the distribution of the surface irregularities of Al ₂ O ₃ is broadened to affect the diameter distribution of the Fe fine particles.

Example 5

(Production of Carbon Nanotube Aggregates)

On a silicon substrate having a SiO ₂ film on its surface (a wafer having a thermal oxide film, a KST material, a SiO ₂ film thickness = 0.5 μm, the thickness of a SiO ₂ film and a silicon substrate = 550 μm), a vacuum deposition apparatus (JEOL, JEE- After the Al thin film (thickness 10 nm) was formed by 4X Vacuum Evaporator, oxidation treatment was performed at 450 ° C for 1 hour. In this way, an Al ₂ O ₃ film was formed on the silicon substrate. On this Al ₂ O ₃ film, a thin Fe film (thickness 2 nm) was deposited by a sputtering device (manufactured by ULVAC, RFS-200) to further form a catalyst layer.

Next, the silicon substrate having a catalyst layer was cut, placed in a 30 mm phi quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas held at a moisture content of 330 ppm was allowed to flow through the quartz tube for 30 minutes to replace the tube. Thereafter, the tube was gradually heated to 765 ° C for 30 minutes using an electric tube furnace, and stabilized at 765 ° C. After standing at 765 ° C. for 10 minutes, helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) mixed gas was charged into the tube while the temperature was maintained, and left for 60 minutes to grow carbon nanotubes on the substrate. To obtain a carbon nanotube aggregate (5).

The length of the carbon nanotube aggregate 5 was 1073 μm.

The layer number distribution of the carbon nanotube aggregate 5 is shown in FIG. 10. As shown in FIG. 10, the mode existed in 4th floor and 8th floor, and the relative frequency was 20%, respectively.

The results are summarized in Table 3.

(Measurement of Shear Adhesion)

The carbon nanotubes (single layer carbon nanotubes) with which the carbon nanotube assembly 5 is equipped are taken out with a spatula, and one end is pressed against glass (MATSUNAMI slide glass 27 mm x 56 mm), and the carbon nanotube assemblies with the substrate 5 )

Shear adhesive force was measured using the carbon nanotube aggregate 5 with a base material as a sample (measurement method (A)). Shear adhesive force, was 42.6N / cm ² at 40.7N / cm ^2, 250 ℃ at room temperature.

The results are summarized in Table 3.

Example 6

Carbon nanotubes were prepared in the same manner as in Example 5 except that a mixed gas of helium / hydrogen / ethylene (105/80 / 15sccm, moisture content 350ppm) was charged into a quartz tube and left for 20 minutes to grow a carbon nanotube on a substrate. The tube assembly 6 was produced.

The carbon nanotube aggregate 6 had a length of 357 µm.

The layer number distribution of the carbon nanotube aggregate 6 is shown in FIG. As shown in FIG. 11, the mode existed in 4th floor and 8th floor, and the relative frequency was 20%, respectively.

In the same manner as in Example 5, a carbon nanotube aggregate (6) with a substrate was obtained.

Shear adhesion was measured similarly to Example 5 using the carbon nanotube assembly 6 with a base material as a sample (measurement method (A)). Shear adhesive force, was 30.3N / cm ² at 34.6N / cm ^2, 250 ℃ at room temperature.

The results are summarized in Table 3.

[Comparative Example 4]

Shear adhesive force was measured similarly to Example 5 using the general purpose adhesive (made by Nitto Electric Co., Ltd., 31B) as a sample (measurement method (A)). Shear adhesive force, was 33.2N / cm ² at 65.3N / cm ^2, 250 ℃ at room temperature.

The results are summarized in Table 3.

In Examples 5 and 6, the shear adhesive force with respect to the glass surface in 250 degreeC atmosphere was 0.8-1.2 times the shear adhesive force with respect to the glass surface at room temperature. On the other hand, when the general purpose adhesive was used like the comparative example 4, the shear adhesive force with respect to the glass surface in 250 degreeC atmosphere is less than 0.8 times the shear adhesive force with respect to the glass surface at room temperature, and the drastic fall of adhesive force was seen.

Example 7

The polypropylene resin (30 micrometers in thickness made by Asahi Yangji Pulp Co., Ltd.) was heated at 200 degreeC on the hotplate, and was melted. One end (upper end) of the carbon nanotube aggregate 5 formed in the vertical orientation on the substrate obtained in Example 5 was pressed onto the molten polypropylene resin, and then cooled to room temperature and fixed. Thus, the carbon nanotube aggregate (5 ') with a base material was obtained.

Shear adhesion was measured using the carbon nanotube aggregate (5 ') with a base material as a sample (measurement method (B)). Shear adhesion, surface free energy of shear adhesive strength A for an adherend (glass) of ^{64.4mJ / m 2 43.4N / cm 2} , the surface free energy of shear adhesive strength for an adherend (PP plate) of 29.8mJ / m ² B Was 38.7 N / cm ² .

The results are summarized in Table 4.

Example 8

The polypropylene resin (30 micrometers in thickness made by Asahi Yangji Pulp Co., Ltd.) was heated at 200 degreeC on the hotplate, and was melted. One end (upper end) of the carbon nanotube aggregate 6 formed by vertically orientating the substrate obtained in Example 6 was pressed onto a molten polypropylene resin, and then cooled to room temperature and fixed. Thus, the carbon nanotube aggregate (6 ') with a base material was obtained.

Shear adhesion was measured using the carbon nanotube aggregate 6 'with a substrate as a sample (measurement method (B)). Shear adhesion force is the shear adhesion force B to the adherend (PP plate) of 36.5 N / cm ² and the surface free energy of 29.8 mJ / m ² to the adherend (glass) of surface free energy 64.4 mJ / m ² . Was 40.7 N / cm ² .

The results are summarized in Table 4.

[Comparative Example 5]

The shear adhesive force was measured using the general purpose adhesive (made by Nitto Electric Co., Ltd., 31B) used in the comparative example 4 as a sample (measurement method (B)). Shear adhesion force is the shear adhesion force B to the adherend (PP plate) of 65.0 N / cm ² and the surface free energy of 29.8 mJ / m ² to the adherend (glass) having a surface free energy of 64.4 mJ / m ² . Was 37.0 N / cm ² .

The results are summarized in Table 4.

Examples 7 and 8 in the surface free energy of the shear adhesive strength at room temperature for the adherend (glass) of 64.4mJ / m ² A, the surface free energy at room temperature for the adherend (PP plate) of 29.8mJ / m ² When the shear adhesive force of was B, the value of B / A was 0.8-1.2. On the other hand, Comparative Examples of the case where a general-purpose pressure-sensitive adhesive as shown in FIG. 5, the surface free energy of an adherend of the shear adhesive strength at room temperature for the adherend (glass) of 64.4mJ / m ² A, the surface free energy 29.8mJ / m ² When the shear adhesive force at room temperature with respect to (PP plate) was made into B, the value of B / A was less than 0.8 times, and the fall of the adhesive force was seen significantly.

Example 9

(Production of Carbon Nanotube Aggregates)

Vacuum vapor deposition apparatus (JEEOL, JEE-4X) on a silicon substrate having a SiO ₂ film on its surface (a wafer having a thermal oxide film, a KST material, a SiO ₂ film thickness = 1 μm, and a thickness of a SiO ₂ film and a silicon substrate = 550 μm). After the Al thin film (thickness 10 nm) was formed by a vacuum evaporator, oxidation treatment was performed at 450 ° C. for 1 hour. In this way, an Al ₂ O ₃ film was formed on the silicon substrate. On this Al ₂ O ₃ film, a thin Fe film (thickness 2 nm) was deposited by a sputtering device (manufactured by ULVAC, RFS-200) to further form a catalyst layer.

Next, the silicon substrate having a catalyst layer was cut, placed in a 30 mm phi quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm was allowed to flow through the quartz tube for 30 minutes, thereby replacing the inside of the tube. Thereafter, the tube was gradually heated to 765 ° C for 30 minutes using an electric tube furnace, and stabilized at 765 ° C. After standing at 765 ° C. for 10 minutes, helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) mixed gas was charged into the tube while the temperature was maintained, and the carbon nanotubes were grown on the substrate for 35 minutes. To obtain a carbon nanotube aggregate (9).

The length of the carbon nanotube aggregate 9 was 680 μm.

(Measurement of Shear Adhesion)

The polypropylene resin (30 micrometers in thickness made by Asahi Yangji Pulp Co., Ltd.) was heated at 200 degreeC on the hotplate, and was melted. One end (upper end) of the carbon nanotubes formed by vertically aligning the substrate was pressed onto a molten polypropylene resin, and then cooled to room temperature and fixed. In this way, the carbon nanotube aggregate (9) with the substrate was obtained.

Using the carbon nanotube aggregate 9 with a substrate as a sample, the shear adhesive force was measured at 25 ° C (measurement method (A)). Shear adhesion was 44.60 N / cm ² .

(Non-pollution evaluation)

In a clean room of class 10, the carbon nanotube aggregate 9 with the substrate was reciprocated by one reciprocation and bonded to a semiconductor wafer having a diameter of 4 inches and a thickness of 500 µm. After 1 hour, peeling was performed with a 180 ° peel. The number of particle contaminants having a size of 0.28 μm or more remaining on the peeling surface was measured by a laser surface inspection device (LS-5000, manufactured by Hitachi Electronics Engineering). The number of particles of 0.28 micrometers or more remaining on the peeled semiconductor wafer was 22/4 inch wafers.

In addition, the 180 degree peel in the said non-pollution evaluation was measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece was the carbon nanotube assembly (9) with a base material, and crimping | bonding was performed by carrying out 1 round of 5 kg rollers, and measured by the temperature of 23 +/- 2 degreeC, humidity of 65 +/- 5% RH, and peeling rate of 300 mm / min.

(Peel peel evaluation)

As a light peeling evaluation, the 180 degree peel was measured. The 180 degree peel as a light peelability evaluation was measured by the tensile compression tester (Minebase "TG-1kN") according to the adhesive force (180 degree peeling method) of JIS C 2107. However, the test piece was a carbon nanotube assembly 9 having a substrate having a width of 20 mm, and a crimping was performed by using a silicon wafer (bare wafer, P-type, KST product) as a test plate by reciprocating one roller of 1 kg, and at a temperature of 23. It measured at +/- 2 degreeC, humidity 65 +/- 5% RH, and peeling speed | rate 300mm / min. As a result, the 180 ° peel was 0.95 N / 20 mm.

Industrial availability

The fibrous columnar structure assembly of the present invention can be suitably used as an adhesive since it has excellent adhesive properties. Moreover, it can also be used as a protective sheet at the time of a process of a semiconductor wafer, for example.

10: fibrous columnar structure assembly
1: description
2: fibrous columnar structure

Claims (9)

A plurality of fibrous columnar structures,
The fibrous columnar structure is a carbon nanotube, the carbon nanotube is a carbon nanotube having a plurality of layers,
The distribution width of the layer number distribution of the carbon nanotubes having the plurality of layers is 10 to 30 layers, the relative frequency of the mode of the layer number distribution is 25% or less, the maximum layer number is 5 to 30 layers, and the minimum layer number is 1 to 10 layers. Layered,
A fibrous columnar structure assembly used for an adhesive member, which is a carbon nanotube assembly. The method according to claim 1,
A fibrous columnar structure assembly, wherein the shear adhesion to the glass surface in a 250 ° C. atmosphere is 0.8 to 1.2 times the shear adhesion to the glass surface at room temperature. The method according to claim 1 or 2,
A shear adhesion force at room temperature to an adherend of surface free energy a is A, and a shear adhesion force at room temperature to an adherend of surface free energy b having a difference of 25 mJ / m ² or more from surface free energy a is B (provided that a > b) A fibrous columnar structure assembly having a B / A value of 0.8 to 1.2. The method according to claim 1 or 2,
The fibrous columnar structure assembly in which the mode of the said layer number distribution exists in the range of 2 layer number to 10 layer number of layers. The method according to claim 1 or 2,
A fibrous columnar structure assembly in which the carbon nanotubes having the plurality of layers include carbon nanotubes having a length of 300 μm or more. The method according to claim 1 or 2,
A fibrous columnar structure assembly in which the carbon nanotubes having the plurality of layers are oriented in the longitudinal direction. The method according to claim 1 or 2,
A fibrous columnar structure assembly having a shear adhesion of at least 15 N / cm ² to a glass surface at room temperature. The method according to claim 1 or 2,
A fibrous columnar structure assembly further comprising a substrate, wherein one end of the carbon nanotube is fixed to the substrate. The adhesive member using the fibrous columnar structure assembly of Claim 1 or 2.

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